Strong doping reduction on wafer-scale CVD graphene devices via Al2O3ALD encapsulation.

We present the electrical characterization of wafer-scale graphene devices fabricated with an industrially-relevant, contact-first integration scheme combined with Al2O3encapsulation via atomic layer deposition. All the devices show a statistically significant reduction in the Dirac point position,Vcnp, from around +47 V to between -5 and 5 V (on 285 nm SiO2), while maintaining the mobility values. The data and methods presented are relevant for further integration of graphene devices, specifically sensors, at the back-end-of-line of a standard CMOS flow.

Ground-State Spin Blockade in a Single-Molecule Junction.

It is known that the quantum mechanical ground state of a nanoscale junction has a significant impact on its electrical transport properties. This becomes particularly important in transistors consisting of a single molecule. Because of strong electron-electron interactions and the possibility of accessing ground states with high spins, these systems are eligible hosts of a current-blockade phenomenon called a ground-state spin blockade. This effect arises from the inability of a charge carrier to account for the spin difference required to enter the junction, as that process would violate the spin selection rules. Here, we present a direct experimental demonstration of a ground-state spin blockade in a high-spin single-molecule transistor. The measured transport characteristics of this device exhibit a complete suppression of resonant transport due to a ground-state spin difference of 3/2 between subsequent charge states. Strikingly, the blockade can be reversibly lifted by driving the system through a magnetic ground-state transition in one charge state, using the tunability offered by both magnetic and electric fields.

Phase Transitions in Spin-Crossover Thin Films Probed by Graphene Transport Measurements.

Future multifunctional hybrid devices might combine switchable molecules and 2D material-based devices. Spin-crossover compounds are of particular interest in this context since they exhibit bistability and memory effects at room temperature while responding to numerous external stimuli. Atomically thin 2D materials such as graphene attract a lot of attention for their fascinating electrical, optical, and mechanical properties, but also for their reliability for room-temperature operations. Here, we demonstrate that thermally induced spin-state switching of spin-crossover nanoparticle thin films can be monitored through the electrical transport properties of graphene lying underneath the films. Model calculations indicate that the charge carrier scattering mechanism in graphene is sensitive to the spin-state dependence of the relative dielectric constants of the spin-crossover nanoparticles. This graphene sensor approach can be applied to a wide class of (molecular) systems with tunable electronic polarizabilities.

Transport Properties of a Two-Dimensional PbSe Square Superstructure in an Electrolyte-Gated Transistor.

Self-assembled nanocrystal solids show promise as a versatile platform for novel optoelectronic materials. Superlattices composed of a single layer of lead-chalcogenide and cadmium-chalcogenide nanocrystals with epitaxial connections between the nanocrystals, present outstanding questions to the community regarding their predicted band structure and electronic transport properties. However, the as-prepared materials are intrinsic semiconductors; to occupy the bands in a controlled way, chemical doping or external gating is required. Here, we show that square superlattices of PbSe nanocrystals can be incorporated as a nanocrystal monolayer in a transistor setup with an electrolyte gate. The electron (and hole) density can be controlled by the gate potential, up to 8 electrons per nanocrystal site. The electron mobility at room temperature is 18 cm2/(V s). Our work forms a first step in the investigation of the band structure and electronic transport properties of two-dimensional nanocrystal superlattices with controlled geometry, chemical composition, and carrier density.

Exchange Coupling Inversion in a High-Spin Organic Triradical Molecule.

The magnetic properties of a nanoscale system are inextricably linked to its local environment. In adatoms on surfaces and inorganic layered structures, the exchange interactions result from the relative lattice positions, layer thicknesses, and other environmental parameters. Here, we report on a sample-dependent sign inversion of the magnetic exchange coupling between the three unpaired spins of an organic triradical molecule embedded in a three-terminal device. This ferro-to-antiferromagnetic transition is due to structural distortions and results in a high-to-low spin ground-state change in a molecule traditionally considered to be a robust high-spin quartet. Moreover, the flexibility of the molecule yields an in situ electric tunability of the exchange coupling via the gate electrode. These findings open a route to the controlled reversal of the magnetic states in organic molecule-based nanodevices by mechanical means, electrical gating, or chemical tailoring.

Transition from Strong to Weak Electronic Coupling in a Single-Molecule Junction.

We have investigated charge transport in single-molecule junctions using gold nanoelectrodes at room and cryogenic (10 K) temperatures. A statistical analysis of the low-bias conductance, measured during the stretching of the molecular junctions, shows that the most probable single-molecule conductance is insensitive to the temperature as expected for off-resonant coherent transport. Low-temperature current-voltage measurements show that these junction conformations have a smooth tunnelinglike shape. While separating the electrodes further we find that, in about one-fourth of the cases, the junction switches in an abrupt way to a configuration with I-V characteristics exhibiting a gap around zero bias and resonances at finite bias. The analysis of the I-V shape and of the conductance distance dependence suggests a stretching-induced transition from the strong to the weak electronic coupling regime. The transition involves a large renormalization of the injection barrier and of the electronic coupling between the molecule and the electrodes.

Gate Controlled Photocurrent Generation Mechanisms in High-Gain In2Se3 Phototransistors.

Photocurrent in photodetectors incorporating van der Waals materials is typically produced by a combination of photocurrent generation mechanisms that occur simultaneously during operation. Because of this, response times in these devices often yield to slower, high gain processes, which cannot be turned off. Here we report on photodetectors incorporating the layered material In2Se3, which allow complete modulation of a high gain, photogating mechanism in the ON state in favor of fast photoconduction in the OFF state. While photoconduction is largely gate independent, photocurrent from the photogating effect is strongly modulated through application of a back gate voltage. By varying the back gate, we demonstrate control over the dominant mechanism responsible for photocurrent generation. Furthermore, because of the strong photogating effect, these direct-band gap, multilayer phototransistors produce ultrahigh gains of (9.8 ± 2.5) × 10(4) A/W and inferred detectivities of (3.3 ± 0.8) × 10(13) Jones, putting In2Se3 among the most sensitive 2D materials for photodetection studied to date.

Pick-up and drop transfer of diamond nanosheets.

Nanocrystalline diamond (NCD) is a promising material for electronic and mechanical micro- and nanodevices. Here we introduce a versatile pick-up and drop technique that makes it possible to investigate the electrical, optical and mechanical properties of as-grown NCD films. Using this technique, NCD nanosheets, as thin as 55 nm, can be picked-up from a growth substrate and positioned on another substrate. As a proof of concept, electronic devices and mechanical resonators are fabricated and their properties are characterized. In addition, the versatility of the method is further explored by transferring NCD nanosheets onto an optical fiber, which allows measuring its optical absorption. Finally, we show that NCD nanosheets can also be transferred onto two-dimensional crystals, such as MoS2, to fabricate heterostructures. Pick-up and drop transfer enables the fabrication of a variety of NCD-based devices without requiring lithography or wet processing.

Image effects in transport at metal-molecule interfaces.

We present a method for incorporating image-charge effects into the description of charge transport through molecular devices. A simple model allows us to calculate the adjustment of the transport levels, due to the polarization of the electrodes as charge is added to and removed from the molecule. For this, we use the charge distributions of the molecule between two metal electrodes in several charge states, rather than in gas phase, as obtained from a density-functional theory-based transport code. This enables us to efficiently model level shifts and gap renormalization caused by image-charge effects, which are essential for understanding molecular transport experiments. We apply the method to benzene di-amine molecules and compare our results with the standard approach based on gas phase charges. Finally, we give a detailed account of the application of our approach to porphyrin-derivative devices recently studied experimentally by Perrin et al. [Nat. Nanotechnol. 8, 282 (2013)], which demonstrates the importance of accounting for image-charge effects when modeling transport through molecular junctions.

Evidence of an Off-Resonant Electronic Transport Mechanism in Helicenes.

Helical molecules have been proposed as candidates for producing spin-polarized currents, even at room conditions, due to their chiral asymmetry. However, describing their transport mechanism in single molecular junctions is not straightforward. In this work, we show the synthesis of two novel kinds of dithia[11]helicenes to study their electronic transport in break junctions among a series of three helical molecules: dithia[n]helicenes, with n = 7, 9, and 11 molecular units. Our experimental measurements and clustering-based analysis demonstrate low conductance values that remain similar across different applied voltages and molecules. Additionally, we assess the length dependence of the conductance for each helicene, revealing an exponential decay characteristic of off-resonant transport. This behavior is primarily attributed to the misalignment between the energy levels of the molecule-electrodes system. The length dependence trend described above is supported by ab initio calculations, further confirming an off-resonant transport mechanism.

Hydrogen termination of CVD diamond films by high-temperature annealing at atmospheric pressure.

A high-temperature procedure to hydrogenate diamond films using molecular hydrogen at atmospheric pressure was explored. Undoped and doped chemical vapour deposited (CVD) polycrystalline diamond films were treated according to our annealing method using a H2 gas flow down to ~50 ml∕min (STP) at ~850 °C. The films were extensively evaluated by surface wettability, electron affinity, elemental composition, photoconductivity, and redox studies. In addition, electrografting experiments were performed. The surface characteristics as well as the optoelectronic and redox properties of the annealed films were found to be very similar to hydrogen plasma-treated films. Moreover, the presented method is compatible with atmospheric pressure and provides a low-cost solution to hydrogenate CVD diamond, which makes it interesting for industrial applications. The plausible mechanism for the hydrogen termination of CVD diamond films is based on the formation of surface carbon dangling bonds and carbon-carbon unsaturated bonds at the applied tempera-ture, which react with molecular hydrogen to produce a hydrogen-terminated surface.

Laser-thinning of MoS2: on demand generation of a single-layer semiconductor.

Single-layer MoS(2) is an attractive semiconducting analogue of graphene that combines high mechanical flexibility with a large direct bandgap of 1.8 eV. On the other hand, bulk MoS(2) is an indirect bandgap semiconductor similar to silicon, with a gap of 1.2 eV, and therefore deterministic preparation of single MoS(2) layers is a crucial step toward exploiting the large direct bandgap of monolayer MoS(2) in electronic, optoelectronic, and photovoltaic applications. Although mechanical and chemical exfoliation methods can be used to obtain high quality MoS(2) single layers, the lack of control in the thickness, shape, size, and position of the flakes limits their usefulness. Here we present a technique for controllably thinning multilayered MoS(2) down to a single-layer two-dimensional crystal using a laser. We generate single layers in arbitrary shapes and patterns with feature sizes down to 200 nm and show that the resulting two-dimensional crystals have optical and electronic properties comparable to that of pristine exfoliated MoS(2) single layers.

Direct observation of magnetic anisotropy in an individual Fe4 single-molecule magnet.

We study three-terminal charge transport through individual Fe4 single-molecule magnets. Magnetic anisotropy of the single molecule is directly observed by introducing a spectroscopic technique based on measuring the position of the degeneracy point as a function of gate voltage and applied magnetic field. A nonlinear field-dependence is observed which changes by rotating the sample and is, thus, a direct proof of magnetic anisotropy. The sensitivity of this method allows us to observe small changes in the orientation and magnitude of the anisotropy in different charge states. We find that the easy axes in adjacent states are (almost) collinear.

In situ transmission electron microscopy imaging of grain growth in a platinum nanobridge induced by electric current annealing.

We report an in situ transmission electron microscopy (TEM) imaging of grain growth in a Pt nanobridge induced by a high electric current density. The change in morphology at the nanoscale was recorded in real time together with the electrical characterization of the Pt nanobridge. We find a drop in the differential resistance as the voltage across the bridge is increased; TEM inspection shows that this coincides with thermally induced grain growth, indicating that a reduction of grain boundary scattering is the cause of the resistance decrease.

Nonlinear modal interactions in clamped-clamped mechanical resonators.

A theoretical and experimental investigation is presented on the intermodal coupling between the flexural vibration modes of a single clamped-clamped beam. Nonlinear coupling allows an arbitrary flexural mode to be used as a self-detector for the amplitude of another mode, presenting a method to measure the energy stored in a specific resonance mode. The observed complex nonlinear dynamics are quantitatively captured by a model based on coupling of the modes via the beam extension; the same mechanism is responsible for the well-known Duffing nonlinearity in clamped-clamped beams.

Tunable backaction of a DC SQUID on an integrated micromechanical resonator.

We have measured the backaction of a dc superconducting quantum interference device (SQUID) position detector on an integrated 1 MHz flexural resonator. The frequency and quality factor of the micromechanical resonator can be tuned with bias current and applied magnetic flux. The backaction is caused by the Lorentz force due to the change in circulating current when the resonator displaces. The experimental features are reproduced by numerical calculations using the resistively and capacitively shunted junction model.

High-frequency gas effusion through nanopores in suspended graphene.

Porous, atomically thin graphene membranes have interesting properties for filtration and sieving applications. Here, graphene membranes are used to pump gases through nanopores using optothermal forces, enabling the study of gas flow through nanopores at frequencies above 100 kHz. At these frequencies, the motion of graphene is closely linked to the dynamic gas flow through the nanopore and can thus be used to study gas permeation at the nanoscale. By monitoring the time delay between the actuation force and the membrane mechanical motion, the permeation time-constants of various gases through pores with diameters from 10-400 nm are shown to be significantly different. Thus, a method is presented for differentiating gases based on their molecular mass and for studying gas flow mechanisms. The presented microscopic effusion-based gas sensing methodology provides a nanomechanical alternative for large-scale mass-spectrometry and optical spectrometry based gas characterisation methods.

Three-terminal electric transport measurements on gold nano-particles combined with ex situ TEM inspection.

We have fabricated nanometer-spaced electrodes on electron-transparent silicon nitride membranes. A thin Cr/Au layer is evaporated on the backside of the membrane which serves as a gate electrode. Using these devices, we have performed three-terminal electron transport measurements on gold nano-particles at liquid helium temperature. Coulomb Blockade features have been observed and the capacitance to the gate has been extracted. After transport measurements, the Cr/Au back gate is removed and the devices are inspected with a transmission-electron microscope (TEM). TEM inspection reveals the presence of a few nano-particles in the nanogap, which is in agreement with the transport measurements. In addition, the nano-particle size as observed by TEM coincides with the one estimated from the gate capacitance value.

Single-molecule transport in three-terminal devices.

Transport through single molecules has been studied using different test beds. In this paper we focus on three-terminal devices in which a molecule bridges the gap between two gold electrodes and a third electrode-the gate-is able to modulate the conduction properties of the junction. Depending on the electronic coupling, Γ, between the molecule and the gold electrodes, different transport regimes can be distinguished. We show measurements on junctions incorporating different single-molecule systems which demonstrate the distinction between these regimes, as well as the experimental limitations in controlling the exact value of Γ.

Isoreticular two-dimensional magnetic coordination polymers prepared through pre-synthetic ligand functionalization.

Chemical functionalization is a powerful approach to tailor the physical and chemical properties of two-dimensional (2D) materials, increase their processability and stability, tune their functionalities and, even, create new 2D materials. This is typically achieved through post-synthetic functionalization by anchoring molecules on the surface of an exfoliated 2D crystal, but it inevitably alters the long-range structural order of the material. Here we present a pre-synthetic approach that allows the isolation of crystalline, robust and magnetic functionalized monolayers of coordination polymers. A series of five isostructural layered magnetic coordination polymers based on Fe(II) centres and different benzimidazole derivatives (bearing a Cl, H, CH3, Br or NH2 side group) were first prepared. On mechanical exfoliation, 2D materials are obtained that retain their long-range structural order and exhibit good mechanical and magnetic properties. This combination, together with the possibility to functionalize their surface at will, makes them good candidates to explore magnetism in the 2D limit and to fabricate mechanical resonators for selective gas sensing.